Synthesis and Coordination Chemistry of Gold(I) Acetylides. The Solid-State Structure of {[η²-(Ph₃P)AuC⋮CFc]Cu(μ-Cl)}₂

Abstract

The gold(I) acetylide (Ph3P)AuC⋮CC6H3(CH2NMe2)2-3,5 (3) is accessible by the reaction of (Ph3P)AuCl (1) with HC⋮CC6H3(CH2NMe2)2-3,5 (2) in a 1:1 molar ratio. Base-catalyzed desilylation of (Ph3P)AuC⋮CSiMe3 (4) produces the homobimetallic gold(I) species (Ph3P)AuC⋮CAu(PPh3) (5). However, the intermediate formation of (Ph3P)AuC⋮CH could not be evidenced, but is most likely. The coordination chemistry of 5 and (Ph3P)AuC⋮CFc (6) toward different copper(I) halides [CuX] n (7a, X = Cl; 7b, X = Br) is presented. While heterodinuclear 6 affords with equimolar amounts of 7a hexanuclear {[η2-(Ph3P)AuC⋮CFc]Cu(μ-Cl)}2 (8), homobinuclear 5 produces with 7b in a 1:1 molar ratio via ligand exchange polymeric [CuC⋮C] n (10) and mononuclear (Ph3P)AuBr (11). A feasible reaction mechanism for the formation of the latter species is presented. The solid-state structure of 8 is reported. It exhibits a linear array around the gold(I) center and a coplanar arrangement of the Cu2Cl2 and the gold(I) acetylide entities.

Synthesis, solid state structure and spectro-electrochemistry of ferrocene-ethynyl phosphine and phosphine oxide transition metal complexes

“…5 and 6). This coordination geometry is representative for phosphines coordinated to a transition metal complex fragment [16,18]. A comparison of the bond distances and bond angles in 9a and 9b shows that they are in the same range of reported assemblies featuring ferrocene-/ruthenocene-ethynyl, gold(I) alkynyl and PPh 2 building blocks (vide supra) [19].…”

“…15 (9a, 9b), and À37.5 ppm (8b). A shift to lower field occurs upon coordination of the phosphorus atom to a AuCl moiety as given in 8a and 8b [16]. Replacing the chloride ligand in 8a and 8b by a C"CMc unit results in a further downfield shift (Section 4) which is typical for phosphine gold(I) acetylides [16].…”

“…15.7926 (11) 11.9938 (7) 11.9733(8) c (Å) 16.5193 (15) 16.4187 (10) 18.7893 (15) a (°) 96.071 (7) 72.625(5) b (°) 106.794 (7) 79.284 (6) …”

Metall‐Alkinyl‐σ‐Komplexe: Synthesen und Materialien

“…Die strukturelle Charakterisierung ergab, dass die Alkinylliganden durch s-Bindungen an das Au I -Zentrum und durch p-Bindungen an das Cu I -Zentrum gebunden sind. [244] Ebenfalls van Koten et al beschrieben die Synthese einer Serie von Heterometallalkinylen unter Verwendung eines anionischen dreizähnigen NCN-Pinzettenliganden (NCN = 2,6-(NMe 2 ) 2 -C 6 H 3 CH 2 À ). [245] Durch Koordination eines Platinzentrums durch das p-System und zusätz-liche Stabilisierung durch die beiden N-Donorzentren ent- [250] und Trimeren [251] Metall-Alkinyl-s-Komplexe…”

Ligands of biologically active compounds in the nanochemistry of silver and gold (A review)

“…Phenylacetylenides of silver and gold exhibit useful photosemiconductor properties [12]. Recently, Lang et al [13] synthesized gold(I) acetylenides. It is interesting to note that nanocomposites of precious metals on poly(pyrrole) (obtained by electrochemical methods from aqueous solutions) are characterized by a high oxidation level and possess extremely high electrical conductivity [14].…”